Hybrid Double Perovskite Containing Helium: [He2][CaZr]F6

Lloyd, Anthony J.; Hester, Brett R.; Baxter, Samuel J.; Ma, Shangye; Prakapenka, Vitali B.; Tkachev, Sergey N.; Park, Changyong; Wilkinson, Angus P.

doi:10.1021/acs.chemmater.0c04782

Hybrid Double Perovskite Containing Helium: [He₂][CaZr]F₆

Journal Article · Wed Apr 21 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c04782· OSTI ID:1813113

Lloyd, Anthony J. ^[1]; Hester, Brett R. ^[1]; ^[1]; Ma, Shangye ^[1]; Prakapenka, Vitali B. ^[2]; Tkachev, Sergey N. ^[2]; Park, Changyong ^[3]; ^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)
Argonne National Lab. (ANL), Argonne, IL (United States)

Perovskites are of great technological and geological importance, in large part, due to their considerable compositional and structural flexibility. However, the formation of perovskites with neutral species on their A-sites is very unusual. The formation, phase transitions and properties of [He₂][CaZr]F₆, which is the first noble gas containing perovskite to be made, are reported. It is likely that a large family of related materials can also be prepared. On compression in neon, the negative thermal expansion (NTE) material CaZrF₆ amorphizes at ~ 0. 5 GPa. However, on compression in helium at room temperature, gas is inserted into the structure to form a perovskite with helium on the A-site. This suppresses the amorphization until > 3 GPa. Volume versus pressure and Raman measurements suggest that filling of the A-site, to give [He₂][CaZr]F₆, is complete at > 1 GPa. The presence of helium on the A-site in this perovskite leads to a reduction in the magnitude of negative thermal expansion when compared to the parent phase CaZrF₆, likely due to steric impediment of the transverse vibrational motion of fluoride. The helium also leads to considerable stiffening of the structure. At room temperature and ~2.5 GPa, the helium containing hybrid perovskite has a bulk modulus of ~ 47 GPa, whereas CaZrF₆ has a bulk modulus of ~ 40 GPa at ambient. At 15 K, the cubic perovskite [He₂][CaZr]F₆ undergoes a structural phase transition, that likely involves a cooperative tilting of framework octahedra to give a lower-symmetry phase, which is tentatively assigned as tetragonal.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; FG02-94ER14466

OSTI ID:: 1813113

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 9 Vol. 33; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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